Vinylbenzylsulfonium monomers and polymers



United States Patent 01.

3,078,259 VINYLBENZYLSULFONIUM MONOMERS AND POLYMERS Melvin J. Hatch andElmer L. McMaster, Midland, Mich,

assignors to The Dow ChemicalCompany, Midland, Mich., a corporation ofDelaware No Drawing. Filed Oct. 2, 1959, Ser. No. 843,945

37 Claims. (Cl. 26;0,-79.7)

This invention relates to. monomeric and polymeric vinyl sulfoniumcompounds and to a method for their preparation. It more particularlyrelates to water soluble vinylbenzyl sulfonium monomers represented bythe general Formula I, and to water-soluble polymers, corresponding tothe general Formula II, prepared from thesemonomers and pertains to amethod of making the same.

In the Formulae I and II, R is selectedfrom the group consisting ofhydrogen and alkyl radicals contain ing from 1 to 6 carbon atoms, X isan organic sulfurcontaining compound selected from the group consistingof (A) sulfides of the formula, R SR3, wherein R and R each represents amember of the group consisting of (1) alkyl radicals containing from '1to 6 carbon atoms, (2) 'haloalkyl radicals containing from 1 to 6 carbon atoms, (3) hydroxyal-kyl radicals containing from 1 to 6 carbonatoms, (4) aralkyl radicals containing from 7 to 12 carbons, (5) '(CH CHO) CI-I C I-I O,H wherein m is an integer from 1 to 5, (6) C,,H ,,C OH,('7) m iHZ..+1. emu coo alkali metal, (9) -C,,H ,,CONH

and --,-.C H2 cN, Wherein nin substituents (6), (7), (8), (9), (1O),(11) and (12) is an integer from 1 to with the total number of carbonatoms in each of the substituents (6), (7), (8), (9), (10), (11) and(12) not exceeding 6, and where the total number of carbon atoms of theR and R groups attached to a common sulfur atom does not exceed 18 and(B) cyclic thio compounds selected from the group consisting oftetrahydrothiophene, hydroxy substituted tetrahydrothiophene, halosubstituted tetrahydrothiophene, alkyl substituted tetrahydrothiophenewhere alkyl refers to groups containing from 1 to 5 carbon atoms,thiacyclohexane, and l-oxa, 4-thiacyclohexane; and Y is an anion such ascarbonate, chloride,

, 3,078,259 ate ted F b. 19 19.6

2 itra e, a at ulfate, b mide,- dide nditheiik z Z is aninteger greaterthan 10,.

polymer concentration to a loading, equivalent of about 0.02 pound perton of solids in the slimes increased the; solids settling rate to about6.3 inches per minute. Other; polymers corresponding to Formula II aresimilarly use ful. These polymers also can be usedto promote gelformation of aqueous media. The monomers of this invention are made bycontact ing a vinylbenzyl halide with an organic sulfur contaim.

ing compound in the presence or absence of a solvent or non-solventliquid medium. The polymers are pro; duced by subjecting the monomers tothe polymerization methods conventionally used with free radicalcatalyzed aqueous systems, i.e., mass-, emulsion-, and solutionpolymeriza-tion in the presence of actinic light, ultra-violetirradiation, gamma radiation, and peroxides.

In preparing the monomers of this invention, a vinylbenzyl halide suchas the chloride, bromide, or iodide is re acted with an organicsulfur-containing compound asdefined heretofore. Theoretical molarequivalents of the vinylbenzyl halide and the sulfur-containingcompound.

ordinarily are used, although from 50 percent up to 2 00 percentstoichiornetric amounts of the organic sulfur-containing compounds canbe used. An excess of aboutZQfl percent of the stoichiometric valueinsome cases prm motes the formation of the vinylbenzyl sulfonium halidemonomer. This excess of the sulfur containing reactant is recoverablefrom the reaction mixture. If the reactants are liquid, preparation ofthe monomer can be eagried out without use of a solvent, but solventssuchas} water, nitromethane, methanol, ethanol, aceton-itriieand" thelike canv be used. The reaction can be carried'out'; at temperaturesfrom about room temperature up to" about 100 C. but reactiontemperatures frorn' abou t 30 to about C. are preferred. The reactionnormally will he carried out at substantially atmosphericpressures; butsuper-atmospheric pressure sufficient to prevent loss ofvolatilereaetants c be empl yed A r action ime f aboutZ t abQuM h u resuts 'n.- .f9r:.

mation of certain of the monomeric sulfoniumcompounds. However, thisreaction time will vary the different molecular species and reactiontimes of 2 4hour s or more can be employed.

The y ben yl sulfonium. mo ome s. asapr du a h will have a halide anion.

by passing a solution of the monomerinto contae n n on e a e es n n thepr p s l fo m- The concentration of monomer in the reaction solutioni isfound by analyzing the solution for total chloride and The excess ofchloride.

acid hydrogen ion equivalents. over hydrogen ion present is attributableto the vinylbenzyl sulfonium chloride, the amount ofhydrogen-ionindicating the amount of solvolysis ofreactants and prod- 1acts and subsequent formation of hydrogen chloride- If desiredv thi hade fo m. of the monomer-can be converted in a conven 'onal, manner toany one of a number of common anionic forms such as carbonate, nitrate,sulfate, acetate and the like, with:

The monomer can be separated from the reaction mixture by converting itinto an insoluble or slightly soluble salt of the compound, e.g. theperchlorate or the bismuth chloride adduct.

Preparation of the polymers is conveniently carried out by placing asolution containing the monomeric sulfoniurn compound in a glass bomband subjecting this material to ultra-violet irradiation for a period oftime ranging from 4 hours to two weeks or more. Alternatively, otherconventional means of polymerization can be employed as by the use ofother vinyl polymerization catalysts, e.g., gamma radiation, azocatalysts, peroxides, and the like. The polymers are soluble in aqueousmedia, but are insoluble in organic solvents such as acetone, absolutealcohols, aliphatic hydrocarbons, ethylene dichloride and the like. Thereaction solutions of the polymers with or without dilution are useddirectly to flocculate slimes.

While the polymers usually contain at least repeated monomeric units (asexemplified in Formula II by the letter Z which must be greater than10), usually the polymers will have a substantially higher value for Z.The upper limit for Z is dependent on those polymerization media thatcan be provided which will retain the polymer and monomer in a statewhereby further polymerization can be accomplished.

The following examples will serve to further illustrate the invention.

Example 1.Preparation of Vinylbenzyl(Dimethyl) Sulfonium ChlorideMonomer Dimethylsulfide (75 ml.), vinylbenzyl chloride (100 mL, 97.5percent pure) and 125 ml. water were mixed in a 500 milliliter flask andstirred at room temperature (about 20-25 C.) for about 10 hours. Afterthis time the stirring was stopped, and the two layers which formed wereseparated. The weight of the aqueous layer was 106 grams. This solutionupon analysis was found to be 0.5 normal in chloride and 0.05 normal inhydrogen ion which corresponded to 0.45 mole vinylbenzyl(dimethyl)sulfonium chloride.

. The monomer was precipitated as the perchlorate salt from 50 grams ofthe monomer solution by adding an aqueous mixture of 75 milliliters ofsaturated potassium perchlorate solution and 75 milliliters of water tothe aqueous solution of the monomer. The white crystals of the sulfoniumperchlorate were removed from the reaction solution by filtration,washed with water, partially dried in air and then dried to constantweight at about 2 mm. Hg absolute pressure at room temperature overphosphorus pentoxide. Analysis of the product by titration with brominesolution showed that it consisted of monomericvinylbenzyl(dimethyl)sulfonium perchlorate of 99.7 percent purity.

Example 2.-Prepqration of Vinylbenzyl(Dimethyl) Sulfonium ChlorideMonomer in Non-Aqueous Medium A charge of 30.4 g. (0.20 mole) ofvinylbenzyl chloride, 11.6 g. (0.20 mole) of dimethyl sulfide and 50 ml.of absolute ethanol were mixed and allowed to stand for about 18 hoursat room temperature. The reaction solution then was diluted to about 100ml. total volume with additional absolute ethanol. Ten ml. of thismonomer containing solution were mixed with 150 ml. of afilteredsolution of bismuth chloride in absolute ethanol. The monomerprecipitated therefrom as a dense, white gummy precipitate of thebismuth chloride adduct which rapidly became crystalline. This adductwas recrystallized from 100 ml. of boiling methanol and was found to beessentially insoluble in hot aqueous acetic acid or absolute ethanol.

.The recrystallized product was dried over phosphorus pentoxide at lessthan 2 mm. Hg absolute pressure at room temperature and analyzed forconstituent elements. Results of these analyses are as follows:

Example 3.Preparation of Vinylbenzyl(2-Hydroxyethyl,Ethylbenzyl)Sulfonium Chloride A charge of 52 g. ofethylbenzyl(2-hydroxyethyl) sulfide, 37 ml. of vinylbenzyl chloride and28.7 ml. of distilled water were stirred together at about 40 C. forabout 24 hours. The reaction mixture was extracted with 200 ml. ofperchloroethylene followed by two extractions with 25 ml. portions ofmethylene chloride and the resulting 22 ml. aqueous portion separated.The aqueous solution of vinylbenzyl(2-hydroxyethyl,ethylbenzyl)sulfonium chloride was found upon analysis to contain 0.57milliequivalent of chloride ion and 0.44 milliequivalent of hydrogen ionper milliliter of solu tion. There was present 0.13 milliequivalent ofvinylbenzyl(2-hydroxyethyl, ethylbenzyl)sulfonium chloride permilliliter of solution, which indicates about 5 percent of the reactantshad been converted to the vinylbenzyl (Z-hydroxyethyl,ethylbenzyl)sulfonium chloride.

Example 4.-Preparation of Poly[VinyIbenzyl(2-Hydro.xyethylZ-Carbamylethyl)Sulfonium Chloride] Twenty-three grams (0.151 mole) ofvinylbenzyl chloride, 23 g. (0.154 mole) of 2-hydroxyethyl (2-carbamylethyl)sulfide, and 50 ml. of Water were stirred together atabout 35-40 C. for about 48 hours. The reaction solution was extractedfour times with diethyl ether, and after the final extraction, nitrogenwas blown through the residual aqueous solution to strip entrapped ethertherefrom. Analysis of this product reaction solution showed chlorideion of 1.4 milliequivalents and hydrogen ion of 0.123 milliequivalentper milliliter of solution. A 30 ml. sample of the aqueous solution wassealed in a pyrex tube and then exposed to ultra-violet irradiation forfour hours. The viscous solution resulting from this polymerizationtreatment was stirred into acetone in which medium the polymericsolution was insoluble and the polyl'vinylbenzyl (2-hydrovyethyl, 2-carbamylethyl)sulfonium chloride] was transformed into a gummy solid.This solid was separated from the acetone and placed in water whereuponit redissolved. The viscosity of a 0.5 percent solution of the polymerin 2 percent sodium chloride was 1.66 centipoise.

Example 5.-Preparali0n of Vinylbenzyl(Methyl, Pentaethylene Glycol)sulfonium Chloride and Homopolymer A mixture of 21.4 g. (.141 mole) ofvinylbenzyl chloride, 40.7 g. (.158 mole) of CH3S CH CH O) CH CH OH and20 ml. of water were stirred together at 35-40 C. for about 23 hours.Analysis for hydrogen ion (.04 milliequ valent per milliliter solution)and chloride ion (1.7 milhequivalents per milliliter solution) indicatedabout 93 percent conversion to the vinylbenzyl(methyl, pentaethyleneglycol) sulfonium chloride monomer.

The solution was extracted three times with equal volumes of diethylether and stored at about 5-10 C. for two days. A viscous solution wasobtained. The resultmg viscous solution was diluted with about 3 volumesof water. A small amount of insoluble gel was removed from the solutionby filtration. The filtered solution was placed in a pyrex tube, sealedand exposed to ultra-violet irradiation for one day. A viscous,polymeric solution was obtained. This solution was removed from thetube,

precipitated into acetone, and redissolved in water. 'The viscosity of a0.5 percent solution of the poly[vinylbcnzyl (methyl, pentaethyleneglycol) sulfonium chloride] in 2 percent sodium chloride Was 1.34centipoise measured at C.

Example 6.-Preparation of Vinylbenzyl Tetrahydrothiophenium Chloride Achargeof 0.65 g. (7.4 millimoles) of tetrahydrothiophene, 1.0 g. (6.5millimoles) of vinylbenzyl chloride and 3.0 ml. of water were stirredtogether; in a small stoppered flask at approximately C. for about 48hours. The resulting mixture was extracted twice with 15 ml.

portions of diethyl ether and the aqueous portion sepa-, rated. Nitrogenwas blown through the aqueous solution to remove residual entrappedether therefrom. The resulting solution upon analysis for hydrogen andchloride ions was found to contain 0.015 milliequivalent of TABLE IPreparation of Vinylbenzyl Sulfonium Chloride Monomers Reactants Monomerproduction Organic sulfide Aryl- Convervinyl- Water, Reuc- Reacsion tobenzyl milli- Other solvents and reactants tion tion sulfo-Millichloride, liters time, 'temp., nium Structure moles milli hrs. O.cpd.,

moles percent 1 S(CH:)2 3,000 2,000 350 96 18-25 S(CHa) 2 200 200 ml.anhydrous methanol" 18 18-25 39 (HOCH2CH2) 2S 2, 000 2, 000 400 m1.anhydrous methanol. 24 18-25 48 @omsom e5 e5 7 14a Ca. 30 6.7

HOCH2CH2SCH2000N3 70 70 Ca. 91 HaCSCHzCOOH 77.5 77 46 H3CSCHzCOOH 113113 03.100 HaCSCHzC 0C 66 67 5 zCS(CHr)zCH(OH)COONa 93 77 00 (E00CHzCHz) 178 179 26 (HzNOCCH2CHz) 18.. 59 Ca. 70 HaCSOHzCONHz 38 38 Ca.72

@CHzsoHloooH-.- 38.5 as 10 as millimoles NaOH 120 021.40 Ca. 52

HaCSCHzCH2OH 230 230 96 Ca. 40 96 HaCSCHzCHzCON i2 42 27 Ca. 40 Ca. HCSCH CH(OH)CHzOH 111 222 24 0,2.140 87 1 Based on C1 and H+ionconcentrations in final solution. 1 Not analyzed-product directlyconverted to polymer.

TABLE II Preparation of Aryl-Vinylbenzyl Sulfonium Chloride PolymersReactants Polymer production Organic sulfide $5 Remarks benzy 1 Water,Other 501- Total Polymerllzation Result chlorige millivents and reactioncatalyst viscosity Structure. Millimum liters i reactants time molesmoles S (CH; )g 3,000 2,000 350 2 wks... Bubbled air and ac- 1. 9 Soln.viscous; solid pptd. Y tinic light. in ilafeone, redissolved 2,(HOCH2CH2)2S 48 1 498 48 hours. Actinic light and Do,

' bubbled air. HOCH2QH2SCH2000NB. 70 70 100 168 hrs Ultra-violetirradia- Do.

' tion-pyrex bomb. HzCSCHgCOOH 113 113 10 1 1131 111281111. 166 hrsPeroxide Do.

a H QS(OH CH(OII)C0QNa 93 77 100 118 hrs Ultra-violet irradia- 2. 1 Do.-

. tion-sealed tube. (HOOCCH2CH2)2S 178 179' 100. 123 hrs d0 Do. (H NOCCHCHQS 55 59 5O 122 hrs. ..-do n 1.01 Soln. viscous; sticky and gel pptd.in acetone; criiissoolved slowly in 2 HSCS-CHZCONHQ 38 38. 25 148 hrs..do 2. 2 .Soln. viscous; polymer pptd; in acetone, dissolved in water.HsCSCHzCHzOH 230 230 50 168 hrs Actiniic light and per- 1.02 Do 0x1 es.HaCSCH2CH(OH) CHzOH x11 1, 222 30 25 hrs.-. Actiuic light, stirred 1. 06Do irilr the presence 0! 1 0.5 percentsolution in 2-percent aqueoussodium chloride at 25 Q.

In a manner similar to that shown for the foregoing Examples,

orn=cnon=nr and omsoniomoniciaicoon are reacted to form are reacted toform sHn CHFCH CHaS om=onomr and crnnsomo OK are reacted to form GHzCOOKI om=onornoumd on som $0511 are reacted to form are reacted to formCHFOHQCHQCI and OH SCHzCHzCN are reacted to form OHFOHQCHaS OHzOHzCNClll CHFCH CH201 and CIHsS-CHaGHzO CHQGH} are reacted to form are reactedto form CHzBr and S O are reacted to form CHFOH CHIS OBr H: H: om=cncmo1and s are reacted to form CHz=CH CH2S C1 CrHn CoHls CH=CH 011,61 andcmscmcl are reacted to form CHFCH CH2S\ CHzClOl and orn=onomo1 andornsonircfimcmm are reacted to form CH: CH2=CH CH2S\ OH2(CHI)1CHIBIThese monomers can be further polymerized to the correspondingpoly-[vinyl-benzenesulfonium halides].

Various modifications can be made in the present invention withoutdeparting from the spirit or scope thereof for it is understood that Welimit ourselves only as defined in the appended claims:

We claim: 1. A water soluble monomeric vinylbenzyl sulfonium compoundhaving the following formula:

H CH

wherein R is selected from the group consisting of hydrogen and alkylcontaining from 1 to 6 carbon atoms, X is an organic sulfur-containingcompound selected from the group consisting of (A) sulfides of theformula, R SR wherein R and R each represents a member selected from thegroup consisting of (1) alkyl radicals containing from 1 to 6 carbonatoms, (2) haloalkyl radicals contaniing from 1 to 6 carbon atoms (3)hydroxyalkyl radicals containing from 1 to 6 carbon atoms, (4) aralkylradicals containing from 7 to 12 carbon atoms, (5) CH CH O) CH CH OHwhere m is an integer from 1 to 5, (6) C H COOH,

(s) -C H C0O alkali metal, (9)--C H CONH (11) -C H COC H and (12) -C HCN, wherein n in substituents (6), (7), (8), (9), (10), (11) and I9 (12)is an integer from l'to with the total number of carbon atoms in each ofthe substituents (6), (7), (8),

(10) (11) and (12)" not to -exceed 6, 'and where the total number ofcarbonatoms of the R and R3 groups attached to a common sulfur atom-does-not exceed 18; (B)-a member selected from the group consisting oftetrahyd'rothiophene, hydroxy substituted tetrahydrothiophene,halosubstituted tetrahydrothiophene, alkyl substitutedtetrahydrothiophene where alkyl is limited to those groups containingfrom 1 to 5 carbons, thiacyclohexane and 1- oxa, 4-thiacyclohexane; andY is an anion selected from the group consisting of carbonate, chloride,nitrate, acetate, sulfate, bromide and iodide.

2. Viny1benzyl(dimethy1) sulfonium chloride.

3 Vinylbenzyl(di,2-hydroxyethyl) sulfonium chloride.

4. Vinylbenzyl(Z-hydroxyethyl, ethylbenzyl)sulf0nium chloride.

5. Viny1benzyl(benzyl), (methyl) sulfonium chloride.

6. Vinylbenzyl(Z-hydroxyethyl, carboxymethyl, sodium salt) sulfoniumchloride.

7. Viny1benzyl(methyl, chloride.

8. Viny1benzyl(methyl, carbomethoxy methyl) sulfonium chloride.

9. Viny1benzyl(methyl, 2-hydroxy, Z-carboxyethyl, sodium salt) sulfoniumchloride.

10. Vinylbenzyl(di(2-carboxylethyl) sulfonium chloride.

11. Viny1benzyl(di Z-carbamylethyDsulfonium chloride.

12. Viny1benzyl(methyl, carbamylmethyl) sulfonium chloride.

13. Vinylbenzyl (benzyl, carboxymethyl) sulfonium chloride.

14. Viny1benzyl(methyl, chloride.

15. Vinylbenzyl(2-hydroxyethyl, 2-carbamylethyl)sulfonium chloride.

16. Viny1benzyl(methyl, 2,3-dihydroxypropyl)sulfonium chloride.

17. Vinylbenzyl(methyl, pentaethyleneglycol)sulfonium chloride.

18. Vinylbenzyl tetrahydrothiophenium chloride.

19. Viny1benzyl(methyl, 2 hydroxyethyDsulfonium chloride.

20. A process for the preparation of water soluble vinylbenzylsulfoniummonomers which comprises; contacting a Vinylbenzyl halide and an organicsulfur containing compound selected from the group consisting ofsulfides and cyclic thio compounds at temperatures from about 18 C. toabout 100 C. for a period of time sufficient to prepare thecorresponding Vinylbenzyl sulfonium halide.

21. A process for the preparation of water soluble vinylbenzyl sulfoniummonomers which comprises; contacting a Vinylbenzyl halide and an organicsulfur containing compound selected from the group consisting ofsulfides and cyclic thio compounds in an aqueous reaction medium attemperatures from about 18 C. to about 80 C. and at substantiallyatmospheric pressure from about 2 to about 120 hours.

22. A process for the preparation of water soluble vinylbenzyl sulfoniummonomers which comprises; contacting a vinylbenzyl halide and an organicsulfur-containing compound selected from the group consisting ofsulfides and cyclic thio compounds in a polar anhydrous organic solventat temperatures from about 18 C. to about 80 C. and at substantiallyatmospheric pressure from about 2 to about 120 hours.

23. A process for the preparation of water soluble Vinylbenzyl sulfoniummonomers which comprises, contacting a Vinylbenzyl halide with fromabout 50 percent of stoichiometric to about 200 percent ofstoichiometric amounts of an organic sulfur-containing compound selectedfrom the group consisting of sulfides and cyclic thio carboxymethyl)sulfonium 2-carb amyl ethyl) sulfonium compounds at temperatures fromabout 30' to about 40 C.' and atsubstantiallyatmospheric: pressures fora period of time sufficient tozpreparethe corresponding vinylbenzylsulfoniumhalide.

524. A wvater soluble polymerjof at I leastone vinyl- :benzyl sulfoniumcompound which polymer fhas -=the: following formula:

X(Y) jz CH CH O) CHzCHgOH wherein m is an integer from 1 to 5, (6) --C HCOOH, (7 )-C,,H ,,COOC,,H (8)-C,,H ,,COO alkali metal, (9) -C H CONH -OnHtnCL C Harm (11)-C,,H ,,COC,,H and (12)-C H CN, wherein n insubstituents (6), (7), (8), (9), (10), (11) and (12) is an integer from1 to 5 with the total number of carbon atoms in each of the substituents(6), (7), (8), (9), (10), (11) and (12) not to exceed 6, and where thetotal number of carbon atoms of the R and R groups attached to a commonsulfur atom does not exceed 18, and (B) a member selected from the groupconsisting of tetrahydrothiophene, hydroxy-substitutedtetrahydrothiophene, halo-substituted tetrahydrothiophene, alkylsubstituted tetrahydrothiophene where alkyl is limited to those groupscontaining from 1 to 5 carbons, thiacyclohexane and 1-oxa-4-thiacyclohexane; Y is an anion and Z is an integer greater than10.

25. Poly-[vinylbenzyl(dimethyl) sulfonium chloride].

26. Poly [vinylbenzyl(di,2 hydroxyethanoDsulfonium chloride].

27. P-oly-[Vinylbenzyl(Z-hydroxyethyl, carboxymethyl, sodium salt)sulfonium chloride].

28. Poly-[vinylbenzyl(methyl, nium chloride].

29. Poly [vinylbenzyl(methyl, 2-hydroxy-2-carboxyethyl, sodium salt)sulfonium chloride].

30. Poly [vinylbenzy1(di,2 carboxyethyDsulfonium chloride].

31. Poly [vinylbenzyl(di,2-carbamylethyl)sulfonium chloride].

32. Poly [vinylbenzyl(methyl, carbamylmethyl)sulfonium chloride] 33.Poly [vinylbenzyl(methyl, 2-hydroxyethyl)sulfonium chloride].

34. Poly [vinylbenzyl(Z hydroxyethyl, Z-carbamylethyl) sulfoniumchloride] 35. Poly [vinylbenzyl(methyl, 2,3-dihydroxypropyl) sulfoniumchloride].

carboxymethyl) sulfo- References Cited in the file of this patent UNITEDSTATES PATENTS Werntz Oct. 31, 1939 Harris Mar. 19, 1940 Johnston May28, 1957 Hwa July 21, 1959 UNITED STATES PATENT OFFICE CERTIFICATE OFCORRECTION Patent No 3,078,259 February 19 1963 Melvin J. Hatch et a1.

It is hereby certified that error appears in the above numbered patantrequiring correction and that the said Letters Patent should read as:orrected below.

Column 7, lines 25 to 28, the upper right-hand portion of the formulareading read 5 21 5 1 1 lines 38 and 39 for the extreme right-handportion of the formula reading lines 49 to 51 for that portion of theformula reading CH S read CH S same column, lines 59 to 61, the upperleft-hand portion of the formula vreading 111 read (i li column 8, line65, after "(5)" the formula should appear shown below instead of as inthe patent:

(CH CH O) CH CH OI-1 Signed and sealed this 12th day of November 1963;

(SEAL) Attest:

ERNEST W, SWIDER EDWIN L, REYNOLDS Attesting Officer Acting Commissionerof Patents

1. A WATER SOLUBLE MONOMERIC VINYLBENZYL SULFONIUM COMPOUND HAVING THEFOLLOWING FORMULA: